In our ongoing efforts to develop poly(2-oxazoline)s (POx) for biomedical applications, we report on the preparation of defined, star-like hydrophilic Pox. Using pluritriflate initiators, we show, through online kinetic measurements by gas chromatography, that multiple initiating groups are of equal reactivity for the initiation of the polymerization of 2-oxazolines. The overall polymerization rate increases linearly with the number of initiator functions per molecule. Thus, all initiating moieties are of the same reactivity and all arms grow at the same rate. This is crucial for the establishment of a meaningful structure -property relationship for polymers of star architectures.